WO1991012126A1

WO1991012126A1 - Method for improving the paintability of objects fashioned from polyamide/polyolefin alloys

Info

Publication number: WO1991012126A1
Application number: PCT/FR1991/000116
Authority: WO
Inventors: Francis Verzaro
Original assignee: Societe Nationale Elf Aquitaine
Priority date: 1990-02-15
Filing date: 1991-02-14
Publication date: 1991-08-22
Also published as: ES2077218T3; NO913986D0; CA2050486A1; FR2658115B1; KR920700888A; DE69111145D1; EP0468039B1; DE69111145T2; NO300017B1; ATE124906T1; FR2658115A1; JPH04505476A; EP0468039A1; NO913986L

Abstract

A method for improving the paintability of a shaped object of which at least the outer portion is made of a polyamide/polyolefin alloy, wherein an electrical discharge is made to act on a gaz in order to create a cold plasma type reactive gas stream, and the shaped object is brought into contact with the reactive gas stream thereby produced and with an oxygen source in order to oxidize the surface of the shaped object. The method is particularly useful for treating trim for motor vehicles as well as items of garden furniture prior to painting.

Description

Process for improving the ability to paint shaped objects from polyamide / polyolefin alloys 5

The invention relates to a method for improving the ability to paint shaped objects from polyamide / polyolefin alloys.

Polyamide / polyolefin alloys, in particular 0 polyamide / polypropylene alloys, are polymeric materials which are generally obtained by mixing a polyamide component, consisting of one or more polyamides, with a polyolefin component, consisting of one or more polyolefins such as, for example. example, polypropylene, and an agent capable of compatibilizing the two polymer components or alternatively by mixing a polyamide component, consisting of one or more polyamides, with a modified polyolefin component, consisting of one or more polyolefins, in particular 0 polypropylene, of which l at least one has been modified to improve the compatibility of the polyolefin component with respect to the polyamide component. Said alloys present an interesting compromise between the different properties of each of the polymer components. 5 It is known that polyamides are characterized by good thermal resistance, but that their dimensional stability is affected by a relatively high water uptake, while polypropylene, which does not absorb water, has dimensional stability not affected by the humidity level 0 of the ambient air, but has a modest thermal resistance and a dimensional stability lower than that of dry polyamide.

A polyamide / polypropylene alloy will present by

^% against dimensional stability between that of

35 polypropylene and that of dry polyamide, a water recovery close to that of polypropylene and therefore a dimensional stability independent of the humidity level of the adjuvant air and also a satisfactory thermal resistance. Polyamide / polyolefin alloys can be used, in particular, in the automotive industry for the production of appearance parts such as wheel covers and body fenders or in other fields and, in particular, for the production of garden furniture.

For use in the production of automotive appearance parts, a polymer alloy must have, inter alia, good thermal resistance to temperatures of the order of 180 "C., which correspond to the firing temperatures of the paints used for the elements of automobile bodywork, so that said polymer alloy parts can be inserted into a paint line in the same way as metal parts, and also a satisfactory ability to paint.

It is known to produce polyamide / polypropylene alloys having the aforementioned thermal stability for the production of automotive appearance parts, but on the other hand the ability to paint such parts still poses a problem due to insufficient polarity of the surface of the alloy part which results in poor adhesion between the paint coating and said surface. Such adhesion does not meet specifications of the automotive industry and it is necessary to use a surface treatment of said alloy part, before painting, to improve its ability to receive paint.

It has been found that treating the surface of an object shaped from a polyamide / polyolefin alloy using cold plasma, i.e. a reactive gas flow resulting from the action of an electric discharge on a gas, and a source of oxygen constituted a technically effective and economically viable solution to improve the ability to paint said object and, in particular, to make the adhesion between the paint film and the surface of the object conforming to specifications of the automotive industry.

The invention therefore provides a method for improving the ability to paint a shaped object, at least the outer part of which is made of an alloy polyamide / polyolefin, this process being characterized in that an electrical discharge is acted on a gas so as to produce a reactive gas flow of the cold plasma type and the shaped object is brought into contact with the gas flow ^' reagent thus produced and with a source of oxygen to effect oxidation of the surface of the shaped object.

As is known in the art (cf., for example, the KIRK-OTHMER encyclopedia entitled ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, Third Edition, Volume Supplement, page 614), the term "cold plasma" designates an out of equilibrium gas plasma thermodynamics for which the temperature of the electrons is very high compared to the temperature of the other species contained in the plasma, the latter temperature remaining close to ambient temperature.

In the implementation of the method according to the invention, the production of the reactive gas flow by action of the electrical discharge on the gas and the bringing of the shaped object to be treated into contact with the reactive gas flow and with the source of oxygen can be carried out simultaneously in the same treatment zone, it is also possible to produce the reactive gas flow in a first zone, then to bring into contact, in a second zone, the shaped object to be treated with said reactive gas flow and to carry out in a third zone, the contacting of the shaped object, treated by the reactive gas flow, with the source of oxygen. It is also possible simultaneously to produce in the same zone the production of the reactive gas flow and the bringing into contact of the shaped object to be treated with said reactive gas flow, then to carry out in another zone the bringing into contact of

chosen from rare gases, in particular argon, hel um and neon, nitrogen, oxygen, nitrogen oxides, ammonia, carbon dioxide, water vapor, oxygenated compounds volatile organic matter under the conditions of use and mixtures of such gases and / or compounds, in particular air, mixtures of nitrogen and oxygen other than air and mixtures of oxygen and one or more rare gases. The electric discharge can be generated in the gas by using any suitable system for producing an electric discharge operating in direct current, alternating current or pulsed current, the alternating or pulsed current having a frequency ranging from low frequencies, by example 50-60 Hz, at microwave frequencies. The power of the electric discharge generator system can range, for example, from a few watts to a few kwatts.

For the production of the reactive gas flow which can be used in the process according to the invention, the system generating the electric discharge in the gas can be, for example, a direct current system producing an electric discharge which can be of the corona type, a system of AC discharge of the capacitive coupling type between two. electrodes or inductive coupling type or a microwave current electrical discharge system coupled by resonant cavity.

The oxygen source which is brought into contact with the shaped object, simultaneously or subsequently to the contacting of said object with the reactive gas flow (cold plasma), can consist of the gas subjected to the electric discharge, when this gas contains free oxygen and / or an organic oxygenated compound which is volatile under conditions of use. The oxygen source can also consist of a gas containing free oxygen or / and an organic oxygenated compound as mentioned above, which is injected into the contacting zone of the shaped object with the reactive gas flow. . The oxygen source can also consist of atmospheric oxygen when the shaped object is brought into contact with the ambient atmosphere, after said object is brought into contact with the reactive gas flow.

The temperatures for implementing the process according to the invention and in particular the temperatures for bringing the shaped object to be treated into contact with the reactive gas flow are most often equal to the temperature ambient or close to the latter, although it is possible to operate at higher temperatures provided however to remain below the temperatures leading to mechanical deformation of the shaped object.

The pressure in the zone or zones where the method according to the invention is implemented can range from approximately 1 Pa to approximately 10 ⁵ Pa.

The duration of the treatment of the object shaped by the reactive gas flow, that is to say the duration of the maintaining in contact of said shaped object with said reactive gas flow, can range, for example, from 0.1 s to approximately 200 s .

The polyamide / polyolefin alloy, which forms at least the external part of the shaped object to be treated according to the invention and which most often constitutes all of the material of said object, can be chosen from polyamide / polyolefin alloys, which are formed, as indicated above, of a mixture of a polyamide component, consisting of one or more polyamides, with a polyolefin component, consisting of one or more polyolefins, and a co-compatibilizing agent capable of compatibilizing the

alpha-olefin C ₂ -C _¹² "t preferably C ₂ to C _g, in particular polypropylene, polyethylene and ethylene / propylene copolymers.

When the polyamide and polyolefin components of the alloy are compatibilized by using a compatibilizing agent, such an agent can be chosen from the various products offered for this purpose and advantageously from the compatibilizing agents which are described in the citations FR-A- 2629090 and FR-A-2628115. When the polyamide and polyolefin components of the alloy are compatibilized by modification of at least one of the polyolefins present in the polyolefin component, the modified polyolefin can be in particular a polypropylene, a polyethylene or an ethylene / propylene copolymer, on which has grafted functional groups providing an affinity for polyamides, and in particular a maleated polypropylene.

Non-limiting examples of polyamide / polyolefin alloys used to produce the shaped articles, which are treated according to the invention, are in particular the alloys combining a polyamide component, comprising at least one polyamide consisting of copolyamide 6-6, polyamide 6 , polyamide 11 or polyamide 12, with a polyolefin component, comprising at least one polyolefin consisting of polypropylene, polyethylene or ethylene / propylene copolymer and with a compatibilizing agent chosen from those described in the citations FR-A-2629090 and FR-A-2628115 . As examples of polyamide / polyolefin alloys using a modified polyolefin component, mention may be made of alloys associating a maleized polypropylene with at least one polyamide consisting of polyamide 6, polyamide 11, polyamide 12 or copolyamide 6-6.

The polyamide / polyolefin alloys associating a polyamide component with a polyolefin component and with a compatibilizing agent advantageously contain contents in each of these three constituents chosen so that the weight percentages x of the polyamide component, y of the polyolefin component and z of the compatibilizer, expressed relative to the total of the three constituents, have values such as $ 40 $ 80, $ 20 y $ 59.9 and $ 0.1 z $ 30 with x + y + z = 100, preferred values for x, y and z being such that 50 <: x $ 70, 25 $ y $ 55 and 5. $ z $ 15 with x + y + z = 100.

The weight composition indicated above is in particular that of the polyamide / polyolefin alloys for which the polyamide component is formed of at least one polyamide consisting of polyamide 6, polyamide 11, polyamide 12, or copolyamide 6-6, the polyolefin component is formed from at least one polyolefin consisting of polypropylene, polyethylene or ethylene / propylene copolymer and _% the compatibilizing agent is chosen from those described in citations FR-A-2629090 and FR-A-2628115 and in particular in the examples of these citations .

For polyamide / polyolefin alloys resulting from the combination of a polyamide component, for example consisting of at least one polyamide chosen from polyamide 6, polyamide 11, polyamide 12 and copolyamide 6-6, and a modified polyolefin component, by example maleicized polypropylene, the weight percentages u of the component

previously, these objects include, in particular, appearance parts for automobiles such as wheel covers and body fenders, or even garden furniture elements. The invention is illustrated by the following examples given without limitation. EXAMPLE 1;

From four alloys polyamide / polyolefin different compositions, realized plates having a thickness of 3mm ^'by operating by injection molding and is levied on these disc-shaped sample plates having a diameter of 6cm, and then subjected said samples to treatment according to the invention. The alloys used to manufacture the plates were obtained by mixing the constituents in an extruder operating at a temperature sufficient for the mixture to be in the molten state and had the following composition expressed by weight:

. Alloy A: This alloy consisted of 51.3% of a 6-6 copolyamide with a melting point of 265 ^β C, 29.7% of a homopolymer polypropylene with a melting point of 163 ^β C and d 'melt index' equal to 0.4, 9% of a compatibilizing agent consisting of the graft copolymer obtained in Example 1C of the citation FR-A-2629090 and 10% of an additive consisting of a maleic EPR elastomer.

. Alloy B: This alloy contained 59.8% of a 6-6 copolyamide with a melting point of 265 ^β C, 23% of a homopolymer polypropylene with a melting point of 163 * C and a melt index included between 4 and 6, 9.2% of a compatibilizing agent consisting of the graft copolymer obtained in Example 3C of the citation FR-A-2629090 and 8% of an additive consisting of a maleitized EPR elastomer.

. Alloy C: This alloy was formed of 42.7% of a polyamide 6 having a melting point equal to 220 ^β C, of 24.8% of a homopolymer polypropylene having a melting point equal to 163 "C and a melt index between 4 and 6, 7.5% of a compatibilizing agent consisting of the graft copolymer obtained in Example 3C of the citation FR-A-2629090 and 25% of a filler consisting of CaC0 ₃ . • Alloy D: This alloy contained 57% of a polyamide 6 having a melting point of 220 ^β C, 33% of a homopolymer polypropylene having a melting point of 163 ° C and a melting index of between 4 and 6 and 10% of a compatibilizing agent consisting of the graft copolymer obtained in Example 1C of the citation FR-A-2629090.

The processing of the samples was carried out in a capacitive type enclosure, in which were mounted two horizontal electrodes in the form of plates 5 cm apart and each connected to one of the terminals of an alternating current generator external to the enclosure, said generator providing an electric current having a frequency of 20 kHz at a power of 20 or 60 depending on the case. The treatment chamber was further provided with a conduit for supplying a gas which is a precursor of the reactive gas flow opening out near the space between the electrodes and was also connected to the suction of a primary pump. allowing to maintain the desired pressure inside the enclosure. The sample to be treated was placed between the electrodes of the enclosure so as to rest on the lower electrode and therefore said sample was located directly in the zone of action of the reactive gas flow resulting from the action of the discharge. electric, arising between the electrodes when the latter are energized, on the gas injected between said electrodes, said gas being argon in this example.

After a treatment time equal to 30 seconds, the sample treated by the reactive gas flow (plasma

was subjected to an adhesion test after cross-checking carried out according to standard NF T 30-038 entitled "Crossing test paint and varnish sheets ", to determine the adhesion of the lacquer film to the surface of the sample and a score ranging from 0 to 5 was assigned, as defined in the standard, to characterize this adhesion, the corresponding note O to a satisfactory adhesion and being required by the specifications for "painted appearance parts" applications in the automotive industry.

The operating conditions specific to the processing of the samples and the results of the adhesion test after cross-hatching are recorded in Table I.

TABLE I Argon as a precursor gas for the reactive gas flow

Power delivered Note to Alloy by the generator Pressure in the test (Watts) the enclosure (Pa) of adhesion after grid

20 17.3 0 20 30.6 0 20 46.6 0

20 30.6 0 20 46.6 0

B

20 46.6 0 60 46.6 0

20 17.3 0 20 30.6 0 20 46.6 0

20 17.3 0 20 30.6 0 20 46.6 0 As shown in the notes representative of the results of the adhesion tests after cross-hatching, the lacquer film adheres in a satisfactory manner (note 0) to the surface of the various alloy samples, which have been treated by the process according to the invention. Said adhesion meets the requirements of the automotive industry with regard to painted appearance parts.

On the other hand, for control samples of the same geometry obtained from the various alloys A, B, C or D but not treated by the process according to the invention, the score 4 or 5 was assigned in each case as a result of the test adhesion after cross-hatching, which indicates a poor to very poor adhesion of the lacquer film to the control samples. EXAMPLE 2:

Samples produced as indicated in example 1 from alloys A to D were subjected to a treatment according to the invention as indicated in said example, however changing the nature of the gas subjected to the electric discharge to produce the reactive gas flow and by varying the pressure of said gas from one treatment to another. The duration of maintenance of each sample in contact with the reactive gas flow was equal to 30 seconds. The samples treated with the reactive gas flow were removed from the enclosure and subjected to the adhesion test after cross-checking as explained in Example 1.

The operating conditions specific to the treatment of the samples and the results of the adhesion test after cross-checking are collated in table II TABLE II

Precursor gas Power Pressure in Note to flow Alloy delivered to the enclosure test by the reactive gaseous generator (Pa) of adhesion (Watts) after grid pattern

20 17.3 0 20 30.6 0

B 20 46.6 0 20 93.1 0

Oxygen

20 17.3 0 20 30.6 0 20 46.6 0

20 17.3 0

Nitrogen 20 30.6 0 20 46.6 0

20 17.3 0

B 20 30.6 0 20 46.6 0

Air 20 93.1 0

20 17.3 0 20 30.6 0 20 46.6 0

As is apparent from the marks awarded during the adhesion test after cross-checking carried out on the samples treated as indicated in example 2, the use of oxygen, nitrogen or air as precursor gases of the reactive gas flow leads to results comparable to those obtained in Example 1 with argon as a precursor gas, that is to say to a satisfactory adhesion of the lacquer film to the samples treated by the reactive gas flow.

Claims

CLAIMS - Method for improving the ability to paint a shaped object, at least the outer part of which is made of a polyamide / polyolefin alloy, characterized in that an electrical discharge is acted on a gas so to produce a reactive gas flow of cold plasma type and the shaped object is brought into contact with the reactive gas flow thus produced and with a source of oxygen to effect oxidation of the surface of the shaped object. - Method according to claim 1, characterized in that the gas, which is subjected to the action of electric discharge to produce the reactive gas flow, is chosen from rare gases, in particular argon, helium and neon, the nitrogen, oxygen, nitrogen oxides, ammonia, carbon dioxide, water vapor, oxygenated organic compounds volatile under the conditions of use and mixtures of such gases and / or oxygenated compounds, in particular air, mixtures of nitrogen and oxygen other than air and mixtures of oxygen and one or more rare gases. - Method according to claim 1, characterized in that the production of the reactive gas flow by action of the electric discharge on the gas and the contacting of the shaped object to be treated with the reactive gas flow and with the source of oxygen are performed simultaneously in the same treatment area. - Method according to claim 1, characterized in that the reactive gas flow is produced in one zone, then in another zone the contacting of the shaped object to be treated is carried out simultaneously with the reactive gas flow and the source oxygen. - Process according to claim 1, characterized in that the production of the reactive gas flow and the contacting of the shaped object to be treated with said reactive gas flow are carried out simultaneously in the same zone, then another zone bringing the shaped object, treated by the reactive gas flow, into contact with the oxygen source. - Method according to claim 1, characterized in that one produces the reactive gas flow in a first zone, then one carries out in a second zone the contacting of the shaped object to be treated with said reactive gas flow and the in a third zone, the shaped object treated by the reactive gas flow is brought into contact with the oxygen source. - Method according to claim 3 or 4, characterized in that the gas subjected to the electric discharge contains oxygen and in that the oxygen source consists of said gas. - Method according to claim 5 or 6, characterized in that bringing the shaped object, treated by the reactive gas flow, into contact with the oxygen source consists in bringing said object into contact with the ambient atmosphere, the latter playing the role of oxygen source. - Method according to one of claims 1 to 8, characterized in that the generation of the electric discharge in the gas with a view to producing the reactive gas flow uses a DC electric discharge system, a discharge system electric alternating current of the capacitive coupling type between two electrodes or of the inductive coupling type, or alternatively to a microwave discharge electrical system coupling by resonant cavity. - Method according to one of claims 1 to 9, characterized in that the duration of the maintenance in contact of the shaped object with the reactive gas flow ranges from about 0.1s to 200s. - Method according to one of claims 1 to 10, characterized in that the shaped object to be treated consists entirely of the polyamide / polyolefin alloy. - Method according to one of claims 1 to 11, characterized in that the polyamide / polyolefin alloy, which forms at least the external part of the shaped object to be treated, consists of a mixture of a polyamide component, consisting of one or more polyamides, with a polyolefin component, consisting of one or more several polyolefins, and a compatibilizing agent capable of σompatibiliser the two polymer components in the presence. - Method according to one of claims 1 to 11, characterized in that the polyamide / polyolefin alloy, which forms at least the external part of the shaped object to be treated, consists of a mixture of a polyamide component, consisting of one or more polyamides, with a modified polyolefin component, consisting of one or more polyolefins, at least one of which has been modified to improve the compatibility of the polyolefin component with respect to the polyamide component. - Method according to claim 12 or 13, characterized in that the polyamides from which the polyamide component of the alloy is formed are chosen from aliphatic polyamides or copolyamides such as polyamide 6, polyamide 11, polyamide 12, copolyamide 6- 10 , copolyamide 6-9, copolyamide 6-6, polyesteramides, semi-aromatic polyamides and random or block polyethersteramides. - Method according to claim 12 or 14, characterized in that the polyolefins from which the polyolefin component of the alloy is formed are homopolymers or random copolymers or blocks of C ₂ to C ₁₂ alpha-olefins and preferably C ₂ to C ₈ , in particular polypropylene, polyethylene and ethylene / propylene copolymers. - Method according to claim 13, characterized in that the modified polyolefin is a polypropylene, a polyethylene or an ethylene / propylene copolymer on which functional groups have been grafted bringing an affinity for polyamides, said modified polyolefin being in particular a maleic polypropylene . - Method according to claim 12 or 14 or 15 characterized in that, in the polyamide / polyolefin alloy, the weight percentages x of the polyamide component, y of the polyolefin component and z of the agent compatibilizers, expressed in relation to the total of the three constituents, have values such as 404 x $ 80, 20 $ y $ 59.9 and 0.1 $ z $ 30 with x + y + z = 100, said values preferably being such as $ 50 x $ 70, $ 25 y $ 55 and $ 5 z $ 15 with x + y + z = 100. - Method according to claim 13 or 16, characterized in that, in the polyamide / polyolefin alloy, the weight percentages u of the polyamide component and v of the modified polyolefin component, relative to the total of these two components, have values such as 40 $ u $ 80 and 20 $ v $ 60 with u + v = 100, said values preferably being such as 50 $ u $ 70 and 30 $ v $ 50 with u + v = 100. - Method according to one of claims 12 to 18, characterized in that in addition to its main constituents, namely polyamide component, polyolefin component or modified polyolefin component and, if present, compatibilizing agent, the polyamide alloy / polyolefin also contains one or more products chosen from additives such as elastomers of the maleized EPR type, inorganic fillers such as CaCO ₃ , talc and silica, fibrous reinforcing agents such as glass fibers, antioxidants, stabilizers thermal, UV stabilizers. - Method according to one of claims l to 19, characterized in that the shaped object to be treated is a part of appearance for automobile, in particular a wheel cover or a body wing, or even an element of garden furniture . - Shaped object, at least the outer part of which is made of a polyamide / polyolefin alloy, treated by the method according to one of claims 1 to 20, then coated with a paint.